Terphenyl derivative, liquid-crystal composition, and liquid-crystal display element

ABSTRACT

The present invention provides liquid crystalline compounds having a high voltage holding ratio and a low threshold voltage, little variation of these properties depending on temperature change, high Δn, and good compatibility with other liquid crystal materials particularly under a low temperature; liquid crystal compositions containing these crystalline compounds; and liquid crystal display devices comprising these liquid crystal compositions. The liquid crystalline compounds are terphenyl derivatives represented by general formula (1):                    
     wherein R represents a straight or branched alkyl group of 1-20 carbon atoms, and any methylene groups (—CH 2 —) not adjacent each other in each alkyl group may be replaced by oxygen atoms; X represents halogen atom, —OCF 3 , —OCF 2 H, —CF 3 , —CF 2 H or —CFH 2 ; Y 1 , Y 2 , Y 3 , Y 4 , Y 5  and Y 6  independently represents H or F, but at least two of Y 1 , Y 2 , Y 3  and Y 4  represent F; and any atom constituting these compounds may be substituted by its isotope.

TECHNICAL FIELD

The present invention relates to new liquid crystalline compounds andliquid crystal compositions, more particularly, it relates to terphenylderivatives having a fluorine-substituted-1,4-phenylene group, liquidcrystal compositions containing them, and liquid crystal display devicesconstituted by using the liquid crystal compositions.

BACKGROUND ART

The liquid crystal display devices using the liquid crystalline compound(in this description, the term of a liquid crystalline compound is usedas a generic term for a compound exhibiting a liquid crystal phase or acompound not exhibiting a liquid crystal phase but useful as aconstituent of a liquid crystal composition) are broadly used indisplays of clocks, watches, electronic calculators, word processors andthe like. Lately, many researches have been made for a TFT type displayhaving characteristics such as a high contrast and a broad visual fieldangle.

Liquid crystal compositions for TFT need physical properties, such as ahigh voltage holding ratio, low threshold voltage (Vth), littlevariation of these properties depending on temperature, broadtemperature range of liquid crystal layers, excellent compatibility withother liquid crystal materials and low viscosity. Further, thecompositions having a high optical anisotropy (Δn) are useful forimproving the response speed.

For these reasons, as a component constituting the liquid crystallinecompounds having such characteristics, fluorine-substituted liquidcrystalline compounds are preferably used, as described in (1) JapanesePatent Publication 63-13411, (2) Japanese Patent Publication 63-44132,(3) Japanese Patent Laid-open 2-233626, (4) Japanese Patent Laid-open2-501311, (5) Japanese Patent Laid-open 3-500413, (6) Japanese PatentLaid-open 3-504018, (7) Japanese Patent Laid-open 5-502676, (8) JapanesePatent Laid-open 6-504032, (9) GB2257701 and (10) EP439089, manysynthesis methods and researches have been done.

DISCLOSURE OF INVENTION

The present invention aims to provide liquid crystalline compoundshaving a very high voltage holding ratio, a low threshold voltage, verylittle variation of these properties depending on temperature change,high Δn, and good compatibility with other liquid crystal materialsparticularly under a low temperature, liquid crystal compositionscontaining these compounds, and liquid crystal display devicesconstituted by using the liquid crystal compositions.

The present inventors have earnestly studied to resolve the aboveproblems and have completed the studies by obtaining the terphenylderivatives having the above properties. The compounds are representedby general formula (1);

wherein R represents a straight or branched alkyl group of 1-20 carbonatoms, and any methylene groups (—CH₂—) not adjacent each other in eachalkyl group may be replaced by oxygen atoms; X can be a halogen atom,—OCF₃, —OCF₂H, —CF₃, —CF₂H or —CFH₂; Y₁, Y₂, Y₃, Y₄, Y₅ and Y₆independently represents H or F, but at least two of Y₁, Y₂, Y₃ and Y₄represent F;

in which

a) in case of Y₁═Y₂═F, Y₃═Y₄═H and X═F, Y₅═Y₆═F,

b) in case of Y₁═Y₂═F, Y₃═Y₄═H and X═—CF₃ or —CF₂H, Y₅═Y₆═F or Y₅═Y₆═H,

c) in case of Y₁═Y₃═F, Y₂═Y₄═H and X═—CF₃, Y₅═Y₆═F,

d) in case of Y₁═Y₃═F, Y₂═Y₄═H and X═F or —OCF₃, Y₅═F,

e) in case of Y₃═Y₄═F, Y₁═Y₂═H, and X═F, Y₅═Y₆═F,

f) in case of Y₃═Y₄═F, Y₁═Y₂═H and X═—OCF₃ or —CF₃, Y₅═F,

g) in case of Y₁═Y₂═Y₃═F, Y₄═H, and X═Cl, Y₅═Y₆═F,

h) in case of Y₁═Y₂═Y₃═F, Y₄═H and X═F, —CF₃ or —CF₂H Y₅═F, and

i) in case of Y₁═Y₂═Y₃═Y₄═F and X═Cl or —OCF₃, Y₅═F, however, in case ofY₁═Y₂═F and Y₃═Y₄═H, in case of Y₁═Y₃═F and Y₂═Y₄═H, and in case ofY₃═Y₄═F and Y₁═Y₂═H, not X═Cl,

and any atom constituting the compound may be replaced by an isotopethereof.

A part of the compounds represented by general formula (1) are formallyincluded in the compounds described in the above references (6) to (10).However, in these references, there is no description of data such asvalues of physical properties of the compounds of the present invention,and definite or embodied characteristics of these compounds, so that thepresent invention is not suggested.

The compounds represented by general formula (1) can be classified asfollows into (a-1) to (a-6).

R—B(F,F)—B—Q  (a-1)

 R—B(F)—B(F)—Q  (a-2)

R—B-B(F,F)—Q  (a-3)

R—B(F,F)—B(F)—Q  (a-4)

R—B(F)—B(F,F)—Q  (a-5)

R—B(F,F)—B(F,F)—Q  (a-6)

In the formula, R represents as the same meaning as described above, Brepresents a 1,4-phenylene group, B(F) represents a3-fluoro-1,4-phenylene, B(F,F) represents a 3,5-difluoro-1,4-phenylenegroup, and Q represents the following group:

wherein Y₅, Y₆ and X represent as the same meaning as described above.

As described above, in the formula, R represents a straight or branchedalkyl group of 1-20 carbon atoms. As a straight alkyl group, methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, decyl, pentadecyl oreicosyl can be exemplified. As a branched alkyl group, isopropyl,sec-butyl, tert-butyl, 2-methyl-butyl, isopentyl, isohexyl,3-ethyloctyl, 3,8-dimethyltetradecyl or 5-ethyl-5-methylnonadecyl can beexemplified. Further, the branched alkyl group may be optically activegroup, and compounds having such a group are useful as a chiral dopingagents.

Any methylene groups not adjacent each other in the alkyl groups may bereplaced by oxygen atoms, and concretely, alkoxy groups such as methoxy,ethoxy, propoxy, butoxy, pentyloxy and nonyloxy, and alkoxyalkyl groupssuch as methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl,methoxypentyl, methoxyoctyl, ethoxymethyl, ethoxyethyl, ethoxypropyl,ethoxyhexyl, propoxymethyl, prop oxyethyl, prop oxypropyl, propoxypentyl, butoxymethyl, butoxyethyl, butoxybutyl, pentyloxymethyl,pentyloxybutyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl,heptyloxymethyl and octyloxymethyl can be exemplified.

Although the liquid crystalline compounds of the present inventionrepresented by general formula (1) may be prepared by a method of commonorganic synthesis, as an example, the compounds may be easily preparedby the following method.

wherein R, Y₁-Y₆ and X have the same meaning as described above, Xa andXb are halogen atoms.

Namely, as shown in scheme 1, in mixed solvent of three ingredients;toluene, xylene or the like, alcohol such as ethanol, and water; halogencompound (2) and dihydroxyboran derivative (3) can be reacted in thepresence of a base such as K₂CO₃ or Na₂CO₃ and a catalyst such ascarbon-carried palladium (Pd—C), Pd(PPh₃)₄ or PdCl₂(PPh₃)₂ to producecompound (1) of the present invention. Further, as shown in scheme 2,after reacting halogen compound (2) with a lithium compound such asn-BuLi or sec-BuLi and a zinc compound such as ZnCl₂ or ZnBr₂, thereactant may be reacted with halogen compound (4) to obtain the abovecompound (1).

In the insertion of substituent X into the benzene ring, a raw material,in which X has been previously inserted, can be used, or, X can beeasily inserted into by a well-known reaction at any step. Embodiedexamples are shown in the following. (In the following formulas, Rxshows the following group.)

wherein R, and Y₁-Y₄ show the same meaning as described above.

wherein Y₅ and Y₆ show the same meaning as described above.

Namely, as shown in scheme 3, compound (5) and a lithium compound suchas n-butyllithium and iodine are reacted to obtain compound (6).Compound (6) and sodium trifluoroacetate/copper iodide (I) (G. E. Carret al., Journal of the Chemical Society Perkin Trans Actions I, 921(1988)) or methyl fluorosulfonyldifluoro acetate/copper iodide (I) (Q.Y. Chen et al., Journal of the Chemical Society Chemical Communications,705 (1989)) can be reacted to obtain trifluoromethyl compound (7).

As shown in scheme 4, compound (5), a lithium compound such asn-butyllithium, and a formylation agent such as N-formylpiperidine (G. AOlah et al., Angewandte Chemie International Edition in English, 20,878(1981)), N-formylmorpholine (G. A. Olah et al., The Journal ofOrganic Chemistry, 49, 385 (1984)) or dimethylformamide (DMF) (G. Bosset al., Chemich Berichte, 1199(1989)) can be reacted to obtain compound(8), and the reactant can be reacted with a fluorinating agent such asdiethylamino sulfur trifluoride (DAST) (W. J. Middleton et al., TheJournal of Organic Chemistry, 40, 574 (1975), S. Rozen et al.,Tetrahedron Letters, 41, 111 (1985), M. Hudlicky, Organic Reactions, 35,513 (1988), P. A. Messina et al., Journal of Fluorine Chemistry, 42,137(1989)), or morpholino sulfur trifluoride (K. C. Mange et al., TheJournal of Fluorine Chemistry, 4, 405(1989)) to obtain difluoromethylcompound (9).

As shown in scheme 5, after reducing compound (8) with a reducing agentsuch as sodium borohydride (SBH), lithium aluminum hydride (LAH),diisobutylaluminum hydride (DIBAL) or sodium bis(2-methoxyethoxy)aluminum (SBMEA) to obtain compound (10, the compound (10) can bereacted with a fluorinating agent such as DAST to producemonofluoromethyl compound (11).

As shown in scheme 6, compound (12 is changed to xanthate (13) by amethod such as Albert et al. (Synthetic Communication, 19, 547 (1989)).The resulting compound can be fluorinated by a method of Kurohoshi etal. (Tetrahedron Letters, 33, 29, 4173 (1992)) to producetrifluoromethoxy compound (14).

In addition, as shown in scheme 7, compound (12) is fluorinated in asystem of chlorodifluoromethane/sodium hydroxide (Japanese PatentLaid-open 3-500413) to produce difluoromethoxy compound (15). Otherwise,it can be produced by a method of Chen et al. (The Journal of FluorineChemistry, 44, 433 (1989)).

The halogen compound and dihydroxyborane derivative, which are rawmaterials, can be produced by a well-known method of common organicsynthesis, for example, a simple method as shown in the following.

wherein R, X, Xa, Y₁, Y₂, Y₅ and Y₆ show the same meaning as describedabove.

Namely, as shown in scheme 8, by reacting compound (16) with a lithiumcompound such as n-BuLi and iodine or bromine, halogen compound (17) canbe produced.

As shown in scheme 9, by the reaction a grignard reagent prepred fromhalogen compound (18) and magnesium, with a borane derivative such astrimethoxyborane or triisopropyloxyborane, and then by hydrolysis withhydrochloride or the like, dihydroxyborane derivative (19) can beproduced.

The compound, not shown in the schemes, having —O— in group R of generalformula (1) can be produced by reacting a halogen compound and alcoholor phenol in a solvent such as dimethylsulfoxide, DMF,1,2-dimethoxyethane, tetrahydrofurane, hexamethylphosphric acid triamideor toluene in the presence of a base such as sodium amide (J. B. Rightet al., Journal of the American Chemical Society, 70, 3098 (1948)),potassium carbonate (W. T. Olson et al., Journal of the AmericanChemical Society, 69, 2451(1947)), triethylamine (R. L. Merker et al.,The Journal of Organic Chemistry, 25, 5180 (1961)), sodium hydoxide (C.Wilkins, Synthesis, 156 (1973)), potassium hydroxide (J. Rebek et al.,The Journal of Organic Chemistry, 44, 1485 (1979)), barium hydroxide(Kawabe et al., The Journal of Organic Chemistry, 37, 4210 (1972)) andsodium hydride (C. J. Stark, Tetrahedron Letters, 22, 2089 (1981), K.Takai et al., Tetrahedron Letters, 21, 1657 (1980)).

The above reactions are well-known, and if necessary, the other knownreactions can be also used.

The liquid crystalline compounds of the present invention obtained thushave a very high voltage holding ratio, a low threshold voltage, verylittle variation of these properties depending on temperature and highΔn, and these compounds can be easily mixed with various liquid crystalmaterials and have good solubility at a low temperature.

In addition, these liquid crystalline compounds of the present inventionare physically and chemically very stable under common conditions whenthe compounds are used for liquid crystal display devices, and are veryexcellent as a constituent of nematic liquid crystal compositions.

The compounds of the present invention can be preferably used as aconstituent of liquid crystal compositions for TN, STN and TFT.

The liquid crystal compositions of the present invention are describedin the following. The liquid crystal compositions of the presentinvention preferably contain at least one compound represented bygeneral formula (1) at a ratio of 0.1-99.9% by weight to developexcellent characteristic.

wherein R₁ represents an alkyl group of 1-10 carbon atoms, anynonadjacent methylene groups in the said alkyl group may be substitutedby oxygen atoms or —CH═CH—, and any hydrogen atoms in the alkyl groupmay be substituted by fluorine atoms; X₁ represents a fluorine atom, achlorine atom, —OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂, —OCF₂CF₂H or—OCF₂CFHCF₃; L₁ and L₂ independently represent a hydrogen atom or afluorine atom; Z₄ and Z₅ independently represent a 1,2-ethylene group,1,4-butylene group, —COO—, CF₂O—, —OCF₂—, —CH═CH— or a covalent bond,ring B represents trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or1,4-phenylene whose hydrogen atoms may be substituted by fluorine atoms;ring C represents trans-1,4-cyclohexylene, or 1,4-phenylene whosehydrogen atoms may be substituted by fluorine atoms; further, any atomconstituting these compounds may be substituted by its isotope.

wherein R₂ and R₃ independently represent an alkyl group of 1-10 carbonatoms, any nonadjacent methylene groups in the said alkyl group may besubstituted by oxygen atoms or —CH═CH—, and any hydrogen atoms in thealkyl group may be substituted by fluorine atoms; X₂ represents —CNgroup or —C≡C—CN; ring D represents trans-1,4-cyclohexylene,1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; ring Erepresents trans-1,4-cyclohexylene, 1,4-phenylene whose hydrogen atomsmay be substituted by fluorine atoms, or pyrimidine-2,5-diyl; ring Frepresents trans-1,4-cyclohexylene or 1,4-phenylene; Z₆ represents a1,2-ethylene group, —COO— or a covalent bond; L₃, L₄ and L₅independently represent a hydrogen atom or a fluorine atom; b, c and dindependently represent 0 or 1; further, any atom constituting thesecompounds may be substituted by its isotope.

wherein R₄ and R₅ independently represent an alkyl group of carbon atomsof 1-10, any nonadjacent methylene groups in the said alkyl group may besubstituted by oxygen atoms or —CH═CH—, and any hydrogen atoms in thealkyl group may be substituted by fluorine atoms; ring G, ring I andring J independently represent trans-1,4-cyclohexylene,pyrimidine-2,5-diyl, or 1,4-phenylene whose hydrogen atoms may besubstituted by fluorine atoms; Z₇ and Z₈ independently represent —C≡C—,—COO—, —CH₂CH₂—, —CH═CH— or a covalent bond; further, any atomconstituting these compounds may be substituted by its isotope.

More particularly, the liquid crystal compositions provided by thepresent invention are finally obtained by mixing at least one compoundrepresented by general formula (1) as a first component with thecompounds selected from the group comprising of compounds represented bygeneral formula (2)-(9) according to the purpose of the liquid crystalcomposition.

As preferably embodied compounds represented by general formula (2)-(4)which are used in the liquid crystal compositions of the presentinvention, the following compounds are exemplified.

wherein R₁ and X₁ show the same meaning as described above.

The compounds represented by general formula (2)-(4) have positivedielectric anisotropy values, excellent thermal and chemical stability,and are especially useful for preparing liquid crystal compositions forTFT which require high reliability, i.e. high voltage holding ratio andhigh specific resistance.

For the preparation of liquid crystal compositions for TFT, thequantities of the compounds represented by general formula (2)-(4) maybe within the range of 0.1 to 99.9% by weight, preferably 10 to 97% byweight, and more preferably 40 to 95% by weight relative to the totalweight of the liquid crystal composition. The compounds represented bygeneral formula (7)-(9) may further be contained for adjustment ofviscosity.

The compounds represented by general formula (2)-(4) may also be usedfor the preparation of liquid crystal compositions for STN and TN. Thequantities of the compounds are preferably 50% by weight or less.

As the compounds represented by general formula (5) or (6), thefollowing compounds are preferably used.

wherein R₂, R₃ and X₂ represent the same meaning as shown in the above.

The compounds represented by general formula (5) or (6) have highpositive dielectric anisotropy values, and are used especially forlowering the threshold voltage of the liquid crystal composition. Thecompounds are also used for adjusting optical anisotropy values andexpanding the nematic range through, for example, raising clearingpoints. Further, the compounds are used to prepare liquid crystalcompositions for STN and TN to improve the steepness of theirvoltage-transmittance correlation curve.

The compounds represented by general formula (5) or (6) are especiallyuseful for preparing liquid crystal compositions for STN and TN.

When the quantity of the compounds represented by general formula (5) or(6) is increased, the threshold voltage of the liquid crystalcompositions is lowered and the viscosity is increased. Accordingly, solong as the viscosity of the liquid crystal composition satisfiesrequirements, use of such compounds in large quantities is advantageousfor low-voltage operation. The quantity of the compounds represented bygeneral formula (5) or (6), in case of preparation of liquid crystalcompositions for STN or TN, may be within the range of 0.1 to 99.9% byweight, preferably 10-97% by weight, and more preferably 40-95% byweight.

Preferred compounds represented by general formula (7)-(9) may beexemplified below.

wherein R₄ and R₅ represent the same meaning as described above.

The compounds represented by general formula (7)-(9) have small absolutevalues of dielectric anisotropy, and these are nearly neutral. Thecompounds represented by general formula (7) are mainly used foradjusting viscosity and optical anisotropy values. The compoundsrepresented by general formula (8) or (9) are mainly used for expandingthe nematic range through, for example, raising clearing points oradjusting optical anisotropy values.

Increase in the quantity of the compounds represented by general formula(7)-(9) increases the threshold voltage and lowers the viscosity of theliquid crystal composition. Therefore, so long as the threshold voltageof the liquid crystal composition satisfies requirements, use of thecompounds in large quantities is preferred. The quantity of thecompounds represented by general formula (7)-(9), in case of preparationof liquid crystal compositions for TFT, may be preferably 40% by weightor less, more preferably 35% by weight or less. In case of preparationof liquid crystal compositions for STN and TN, it may be preferably 70%by weight or less, and more preferably 60% by weight or less.

Moreover, in the present invention, except in special cases such asliquid crystal compositions for an OCB (Optically CompensatedBirefringence) mode, an optically active compound is normally added tothe liquid crystal composition of the present invention for adjustingrequired twist angle by inducing formation of the helical structure ofthe liquid crystal composition, and for preventing reverse twist.Although any known optically active compounds may be used in the presentinvention for the above purposes, as preferred compounds, the followingoptically active compounds may be exemplified.

In the liquid crystal compositions of the present invention, the pitchof twist is adjusted by addition of these optically active compounds.The pitch of twist is preferably adjusted within the range of 40-200 μmfor liquid crystal compositions for TFT and TN, and 6-20 μm for liquidcrystal compositions for STN. In case of a bistable TN mode, it ispreferably adjusted within the range of 1.5-4 μm. For adjustment of thetemperature dependence of the pitch, two or more optically activecompounds may be added.

The liquid crystal compositions of the present invention are prepared bywell known methods. In general, a method in which various compounds aredissolved in each other at high temperature is used.

Furthermore, the liquid crystal compositions of the present inventionmay be used as those for the guest-host (GH) mode by adding dichroicdyes such as melocyanin, styryl, azo, azomethyne, azoxy, quinophthalon,anthraquinone and tetrazine types. Moreover, the compositions may beused for NCAP, which is prepared by micro-capsulation of a nematicliquid crystal, or for a polymer dispersion liquid crystal device(PDLCD) represented by a polymer network liquid crystal device (PNLCD),which a polymer of tridimensional network structure is prepared inliquid crystal. In addition, the liquid crystal compositions may be usedfor an electrically controlled birefringence (ECB) mode or a dynamicscattering (DS) mode.

The following liquid crystal compositions containing the compounds ofthe present invention can be exemplified. Moreover, the compounds in thecomposition examples and undermentioned working examples are representedby brief symbols in accordance with the rules expressed in the followingtables, and the numbers of the compounds are the same as those in thefollowing examples. Further, in the composition examples and workingexamples, except with previous notice, “%” means “% by weight”.

Left end group Rc C_(a)H_(2a+1)— a- C_(a)H_(2a+1)O— aO-C_(a)H_(2a+1)OC_(b)H_(2b)— aOb- C_(a)H_(2a+1)OC_(b)H_(2b)O— aObO-C_(a−1)H_(2(a−1)+1)C(C_(b)H_(2b+1))HC_(c)H_(2c)— a(b)c-CFH₂C_(a−1)H_(2(a−1))— Fa- CF₂HC_(a−1)H_(2(a−1))— FFa-CF₃C_(a−1)H_(2(a−1))— FFFa- CFH₂C_(a−1)H_(2(a−1))O— FaO-CFH₂C_(a−1)H_(2(a−1))OC_(b)H_(2b)— FaOb- C_(a)H_(2a+1)CFHC_(b)H_(2b)—a(F)b- C_(a)H_(2a+1)CF₂C_(b)H_(2b)— a(FF)b-C_(a)H_(2a+1)CH═CHC_(b)H_(2b)— aVb-C_(a)H_(2a+1)CH═CHC_(b)H_(2b)CH═CHC_(c)H_(2c)— aVbVc-C_(a)H_(2a+1)CH═CHC_(b)H_(2b)OC_(c)H_(2c)— aVbOc-C_(a)H_(2a+1)OC_(b)H_(2b)CH═CHC_(c)H_(2c)— aObVc-CFH₂C_(a−1)H_(2(a−1))CH═CHC_(b)H_(2b)— FaVb- FFC═CHC_(a)H_(2a)— FFVa-F(CN)C═CHC_(a)H_(2a)— FCVa- Bonding group Za˜Zn —(CH₂)_(a)— a —CH₂O—CH₂O —OCH₂— OCH₂ —C₃H₆O— C₃H₆O —OC₃H₆— OC₃H₆ —COO— E —C≡C— T —CH═CH— V—CF₂O— CF₂O —OCF₂— OCF₂ Ring structure Aa˜Ao

B

B(2F)

B(F)

B(Cl)

B(2,3F)

B(2,3Cl)

B(F,F)

B(F,Cl)

H

Py

D

Ch Right end group Rd —F —F —Cl —CL —CN —C —CF₃ —CF3 —OCF₃ —OCF3 —OCF₂H—OCF2H —OCF₂CF₂H —OCF2CF2H —OCF₂CFHCF₃ —OCF2CFHCF3 —C_(w)H_(2w+1) —w—OC_(w)H_(2w+1) —Ow —C_(w)H_(2w)CH═CH₂ —wV—C_(w)H_(2w)CH═CHC_(x)H_(2x+1) —wVx —COOCH₃ —EMe—C_(w)H_(2w)CH═CHC_(x)H_(2x)F —wVxF —CH═CF₂ —VFF —C_(w)H_(2w)CH═CF₂—wVFF —C≡C—CN —TC

Composition Example 1

3-BB(F,F)B(F,F)—F (Compound No. 26) 5.0% 3-B(F)B(F)B(F,F)—F (CompoundNo. 14) 5.0% 3-B(F)B(F,F)B(F)—F (Compound No. 54) 5.0% 1V2-BEB(F,F)—C5.0% 3-HB—C 25.0% 1-BTB-3 5.0% 3-HH-4 11.0% 3-HHB-1 6.0% 3-HHB-3 9.0%3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F)TB-2 6.0%3-HB(F)TB-3 6.0%

Composition Example 2

3-BB(F,F)B(F)—OCF₃ (Compound No. 1) 6.0% 3-B(F)B(F,F)B(F)—CL (CompoundNo. 57) 6.0% V2-HB—C 12.0% 1V2-HB—C 12.0% 3-HB—C 12.0% 3-HB(F)—C 5.0%2-BTB-1 2.0% 3-HH-4 8.0% 3-HH—VFF 6.0% 2-HHB—C 3.0% 3-HHB—C 6.0%3-HB(F)TB-2 8.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 4.0%

Composition Example 3

3-BB(F,F)B(F)—OCF₃ (Compound No. 1) 5.0% 3O1-BEB(F)—C 15.0% 4O1-BEB(F)—C13.0% 5O1-BEB(F)—C 13.0% 2-HHB(F)—C 15.0% 3-HHB(F)—C 15.0% 3-HB(F)TB-24.0% 3-HB(F)TB-3 4.0% 3-HB(F)TB-4 4.0% 3-HHB-1 8.0% 3-HHB—O1 4.0%

Composition Example 4

3-B(F)B(F)B(F,F)—F (Compound No 14) 4.0% 3-B(F)B(F,F)B(F)—CL (CompoundNo. 57) 4.0% 5-PyB—F 4.0% 3-PyB(F)—F 4.0% 2-BB—C 5.0% 4-BB—C 4.0% 5-BB—C5.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0% 6-PyB—O5 3.0% 6-PyB—O6 3.0%6-PyB—O7 3.0% 6-PyB—O8 3.0% 3-PyBB—F 6.0% 4-PyBB—F 6.0% 5-PyBB—F 6.0%3-HHB-1 6.0% 3-HHB-3 8.0% 2-H2BTB-4 5.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0%3-H2BTB-4 5.0%

Composition Example 5

3-B(F)B(F)B(F,F)—F (Compound No. 14) 10.0% 3-BB(F,F)B(F)—OCF₃ (CompoundNo. 1) 4.0% 3-DB—C 10.0% 2-BEB—C 12.0% 3-PyB(F)—F 6.0% 3-HEB—O4 8.0%4-HEB—O2 6.0% 5-HEB—O1 6.0% 3-HEB—O2 5.0% 5-HEB—O2 4.0% 5-HEB-5 5.0%4-HEB-5 5.0% 1O—BEB-2 4.0% 3-HHB-1 6.0% 3-HHEBB—C 3.0% 3-HBEBB—C 3.0%5-HBEBB—C 3.0%

Composition Example 6

3-B(F)B(F,F)B(F)—CFH₂ (Compound No. 71) 3.0% 3-BB(F,F)B(F,F)—F (CompoundNo. 26) 4.0% 3-B(F)B(F,F)B(F)—F (Compound No. 54) 4.0% 3-HB—C 18.0%1O1-HB—C 10.0% 3-HB(F)—C 10.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0%1O1-HH-3 3.0% 2-BTB—O1 3.0% 3-HHB-1 7.0% 3-HHB—F 4.0% 3-HHB—O1 4.0%3-HB—O2 8.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 2-PyBH-3 4.0% 3-PyBH-3 3.0%3-PyBB-2 3.0%

Composition Example 7

3-B(F)B(F)B(F,F)—OCF₂H (Compound No. 18) 5.0% 3-B(F)B(F)B(F,F)—CF₂H(Compound No. 22) 4.0% 3O1-BEB(F)—C 12.0% 1V2-BEB(F,F)—C 10.0% 3-HH—EMe10.0% 3-HB—O2 18.0% 7-HEB—F 2.0% 3-HHEB—F 2.0% 5-HHEB—F 2.0% 3-HBEB—F4.0% 2O1-HBEB(F)—C 2.0% 3-HB(F)EB(F)—C 2.0% 3-HBEB(F,F)—C 2.0% 3-HHB—F4.0% 3-HHB—O1 4.0% 3-HHB-3 13.0% 3-HEBEB—F 2.0% 3-HEBEB-1 2.0%

Composition Example 8

3-B(F)B(F)B(F,F)—F (Compound No. 14) 5.0% 5-BEB(F)—C 5.0% V—HB—C 11.0%5-PyB—C 6.0% 4-BB-3 6.0% 3-HH-2V 10.0% 5-HH—V 11.0% V—HHB-1 7.0%V2-HHB-1 15.0% 3-HHB-1 9.0% 1V2-HBB-2 10.0% 3-HHEBH-3 5.0%

Composition Example 9

3-BB(F,F)B(F,F)—F (Compound No. 26) 4.0% 2O1-BEB(F)—C 5.0% 3O1-BEB(F)—C12.0% 501-BEB(F)—C 4.0% 1V2-BEB(F,F)—C 16.0% 3-HB—O2 10.0% 3-HH-4 3.0%3-HHB—F 3.0% 3-HHB-1 8.0% 3-HHB—O1 4.0% 3-HBEB—F 4.0% 3-HHEB—F 7.0%5-HHEB—F 7.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-HB(F)TB-2 5.0%

Composition Example 10

3-B(F)B(F,F)B(F)—F (Compound No. 54) 8.0% 2-BEB—C 12.0% 3-BEB—C 4.0%4-BEB—C 6.0% 3-HB—C 20.0% 3-HEB—O4 12.0% 4-HEB—O2 8.0% 5-HEB—O1 8.0%3-HEB—O2 6.0% 5-HEB—O2 5.0% 3-HHB-1 7.0% 3-HHB—O1 4.0%

Composition Example 11

3-B(F)B(F,F)B(F)—CL (Compound No. 57) 5.0% 2-BEB—C 10.0% 5-BB—C 12.0%7-BB—C 7.0% 1-BTB-3 7.0% 2-BTB-1 5.0% 1O—BEB-2 10.0% 1O—BEB-5 12.0%2-HHB-1 4.0% 3-HHB—F 4.0% 3-HHB-1 7.0% 3-HHB—O1 4.0% 3-HHB-3 13.0%

Composition Example 12

3-BB(F,F)B(F)—OCF₃ (Compound No. 1)  7.0% 2-HHB(F)—F 17.0% 3-HHB(F)—F17.0% 5-HHB(F)—F 16.0% 2-H2HB(F)—F 10.0% 3-H2HB(F)—F 5.0% 5-H2HB(F)—F10.0% 2-HBB(F)—F 6.0% 3-HBB(F)—F 6.0% 5-HBB(F)—F 6.0%

Composition Example 13

3-BB(F,F)B(F)—OCF₃ (Compound No. 1) 3.0% 3-B(F)B(F,F)B(F)—CL (CompoundNo. 57) 3.0% 7-HB(F)—F 5.0% 5-H2B(F)—F 5.0% 3-HB—O2 10.0% 3-HH-4 5.0%2-HHB(F)—F 10.0% 3-HHB(F)—F 10.0% 5-HHB(F)—F 10.0% 3-H2HB(F)—F 5.0%2-HBB(F)—F 3.0% 3-HBB(F)—F 3.0% 2-H2BB(F)—F 5.0% 3-H2BB(F)—F 6.0%3-HHB-1 8.0% 3-HHB—O1 5.0% 3-HHB-3 4.0%

Composition Example 14

3-BB(F,F)B(F,F)—F (Compound No. 26) 8.0% 3-B(F)B(F)B(F,F)—F (CompoundNo. 14) 8.0% 3-B(F)B(F)B(F,F)—OCF₂H (Compound No. 18) 5.0%3-B(F)B(F)B(F,F)—CF₂H (Compound No. 22) 5.0% 7-HB(F,F)—F 3.0% 3-HB—O27.0% 2-HHB(F)—F 10.0% 3-HHB(F)—F 10.0% 5-HHB(F)—F 10.0% 2-HBB(F)—F 9.0%3-HBB(F)—F 9.0% 2-HBB—F 4.0% 3-HBB—F 4.0% 5-HBB—F 3.0% 3-HBB(F,F)—F 5.0%

Composition Example 15

3-BB(F,F)B(F,F)—F (Compound No. 26) 4.0% 3-B(F)B(F)B(F,F)—F (CompoundNo. 14) 4.0% 3-B(F)B(F,F)B(F)—F (Compound No. 54) 4.0% 7-HB(F,F)—F 4.0%3-H2HB(F,F)—F 12.0% 4-H2HB(F,F)—F 10.0% 5-H2HB(F,F)—F 10.0% 3-HHB(F,F)—F10.0% 4-HHB(F,F)—F 5.0% 3-HH2B(F,F)—F 15.0% 5-HH2B(F,F)—F 10.0%3-HBB(F,F)—F 12.0%

Composition Example 16

3-B(F)B(F)B(F,F)—F (Compound No. 14) 5.0% 3-BB(F,F)B(F)—OCF₃ (CompoundNo. 1) 5.0% 3-BB(F,F)B(F,F)—F (Compound No. 26) 5.0% 3-B(F)B(F,F)B(F)—F(Compound No. 54) 3.0% 7-HB(F,F)—F 5.0% 3-H2HB(F,F)—F 12.0% 3-HHB(F,F)—F10.0% 3-HBB(F,F)—F 10.0% 3-HHEB(F,F)—F 10.0% 4-HHEB(F,F)—F 3.0%5-HHEB(F,F)—F 3.0% 3-HBEB(F,F)—F 5.0% 5-HBEB(F,F)—F 3.0% 3-HDB(F,F)—F15.0% 3-HHBB(F,F)—F 6.0%

Composition Example 17

3-BB(F,F)B(F)—OCF₃ (Compound No. 1) 7.0% 3-B(F)B(F)B(F,F)—F (CompoundNo. 14) 7.0% 3-HB—CL 10.0% 5-HB—CL 4.0% 7-HB—CL 4.0% 1O1-HH-5 5.0%2-HBB(F)—F 8.0% 3-HBB(F)—F 8.0% 4-HHB—CL 8.0% 5-HHB—CL 8.0% 3-H2HB(F)—CL4.0% 3-HBB(F,F)—F 10.0% 5-H2BB(F,F)—F 9.0% 3-HB(F)VB-2 4.0% 3-HB(F)VB-34.0%

Composition Example 18

3-B(F)B(F)B(F,F)—F (Compound No. 14) 4.0% 3-B(F)B(F)B(F,F)—OCF₂H(Compound No. 18) 4.0% 3-BB(F,F)B(F)—OCF₃ (Compound No. 1) 5.0%3-B(F)B(F,F)B(F)—CL (Compound No. 57) 5.0% 3-HHB(F,F)—F 9.0%3-H2HB(F,F)—F 8.0% 4-H2HB(F,F)—F 8.0% 3-HBB(F,F)—F 21.0% 5-HBB(F,F)—F10.0% 3-H2BB(F,F)—F 10.0% 5-HHBB(F,F)—F 3.0% 3-HH2BB(F,F)—F 3.0%5-HHEBB—F 2.0% 1O1-HBBH-4 4.0% 1O1-HBBH-5 4.0%

Composition Example 19

3-B(F)B(F,F)B(F)—CL (Compound No. 57) 2.0% 3-BB(F,F)B(F,F)—F (CompoundNo. 26) 2.0% 3-B(F)B(F)B(F,F)—F (Compound No. 14) 2.0%3-BB(F,F)B(F)—OCF₃ (Compound No. 1) 2.0% 3-B(F)B(F)B(F,F)—OCF₂H(Compound No. 18) 2.0% 5-HB—F 12.0% 6-HB—F 9.0% 7-HB—F 7.0% 2-HHB—OCF₃7.0% 3-HHB—OCF₃ 11.0% 4-HHB—OCF₃ 7.0% 5-HHB—OCF₃ 5.0% 3-HH2B—OCF₃ 4.0%5-HH2B—OCF₃ 4.0% 3-HHB(F,F)—OCF₃ 5.0% 3-HBB(F)—F 10.0% 3-HH2B(F)—F 3.0%3-HB(F)BH-3 3.0% 5-HBBH-3 3.0%

Composition Example 20

3-B(F)B(F,F)B(F)—F (Compound No. 54) 5.0% 3-BB(F,F)B(F)—OCF₃ (CompoundNo. 1) 2.0% 3-B(F)B(F,F)B(F)—CFH₂ (Compound No. 71) 2.0% 5-H4HB(F,F)—F7.0% 5-H4HB—OCF₃ 13.0% 3-H4HB(F,F)—CF₃ 8.0% 5-H4HB(F,F)—CF₃ 8.0% 3-HB—CL6.0% 5-HB—CL 4.0% 2-H2BB(F)—F 5.0% 3-H2BB(F)—F 10.0% 5-HVHB(F,F)—F 5.0%3-HHB—OCF₃ 5.0% 3-H2HB—OCF₃ 5.0% V-HHB(F)—F 5.0% 5-HHEB—OCF₃ 2.0%3-HBEB(F,F)—F 5.0% 5-HH—V2F 3.0%

Composition Example 21

3-B(F)B(F,F)B(F)—CL (Compound No. 57) 3.0% 3-BB(F,F)B(F,F)—F (CompoundNo. 26) 3.0% 3-B(F)B(F)B(F,F)—F (Compound No. 14) 3.0% 2-HHB(F)—F 2.0%3-HHB(F)—F 2.0% 5-HHB(F)—F 2.0% 2-HBB(F)—F 6.0% 3-HBB(F)—F 6.0%5-HBB(F)—F 10.0% 2-H2BB(F)—F 9.0% 3-H2BB(F)—F 9.0% 3-HBB(F,F)—F 25.0%5-HBB(F,F)—F 10.0% 1O1-HBBH-4 5.0% 1O1-HBBH-5 5.0%

BEST MODE FOR CARRYING OUT THE INVENTION

The following examples illustrate the present invention morespecifically. In each example, C shows a crystal, S_(A) shows a smecticA phase, S_(B) shows a smetic B phase, S_(X) shows a smetic phase thatthe phase constitution remains to be analyzed, N shows a nematic phase,Iso shows an isotropic phase, and the unit of phase transitiontemperature is ° C.

EXAMPLE 1

Preparation of 4″-propyl-2′,6′,3-trifluoro-4-trifluoromethoxyterphenyl(in general formula (1), R is C₃H₇; Y₁, Y₂ and Y₆ are each H; Y₃, Y₄ andY₅ are each F; and X is —OCF₃) (compound No.1)

(Step 1) Preparation of 4′-propyl-3,5-difluoro-4-iodobiphenyl

To a solution of 4′-propyl-3,5-difluorobiphenyl 40.0 g (0.17 mol) intetrahydrofuran (THF) 250 ml, n-BuLi 160 ml (0.25 mol) was addeddropwise at a speed to keep −60 ° C or less, and stirred for one hour atthe same temperature. Then, a solution of iodine 78.7 g (0.31 mol) inTHF 300 ml was added dropwise at a speed to keep −60 ° C. or less, andthe mixture was stirred for one hour at the same temperature.

After 1N—HCl 200 ml was added dropwise to the reaction solution, themixture was extracted with heptane 200 ml. The resulting organic layerwas washed three times with dil. NaHCO₃ and three times with water, anddried over anhydrous magnesium sulfate. The solvent was distilled offunder reduced pressure, the residue was purified by silica-gel columnchromatography (eluent: heptane), and the solvent was distilled off toobtain yellow oil. The oil was recrystallized from ethanol to obtain4′-propyl-3,5-difluoro-4-iodobiphenyl 41.5 g. (Yield: 67.4%)

(Step 2) Preparation of4″-propyl-2′,6′,3-trifluoro-4-trifluoromethoxyterphenyl

A mixture of 4′-propyl-3,5-difluoro-4-iodobiphenyl 4.0 g (11.2 mmol)which was obtained at the above step,dihydroxy(3-fluoro-4-trifluoromethoxyphenyl)borane 30 g (14.5 mmol),K₂CO₃ 3.1 g (22.3 mmol), 5% Pd—C 0.4 g, and mixed solvent 30 ml oftoluene/ethanol/water (1/1/1) was heated to reflux for 10 hours. Then,after Pd—C was filtered off, the mixture was extracted with toluene 100ml, and the resulting organic layer was washed with water three timesand dried over anhydrous magnesium sulfate. The solvent was distilledoff under reduced pressure, and the resulting residue was purified bysilica-gel column chromatography (eluent: heptane) to obtain crude4″-propyl-2′,6′,3-trifluoro-4-trifluoromethoxyterphenyl 40 g. Thecompound was recrystallized from a mixed solvent of ethanol/ethylacetate (9/1) to obatin the title compound 2.1 g. (Yield: 47.1%)

The compound shows a liquid crystal phase and the transition temperaturewas C 61.3-61.6 S_(A) 80.4-80.6 Iso.

The structure was supported well by the spectral data.

Mass spectrum analysis: 410 (M⁺) ¹H-NMR (CDCl₃, TMS internal standard)

δ (ppm)

20 0.97 (t, 3H)

1.52-1.81 (m, 2H)

2.65 (t, 2H)

7.18-7.56 (m, 9H)

In the following, the examples using the compounds of the presentinvention as components of the liquid crystal compositions will bedescribed. In each using example, NI represents nematic phase-isotropicphase transition temperature (° C.), Δ∈ represents the value ofdielectric anisotropy, Δn represents the value of optical anisotropy, ηrepresents viscosity (mPa·s) and Vth represents threshold voltage (V).

Further, η was measured at 20° C., and Δ∈, Δn and Vth were measured at25° C., respectively.

EXAMPLE 2

(Using example 1)

The liquid crystal composition (A) comprising the followingcyanophenylcyclohexane type liquid crystal compounds:

4-(trans-4-propylcyclohexyl)benzonitrile 24%4-(trans-4-pentylcyclohexyl)benzonitrile 36%4-(trans-4-heptylcyclohexyl)benzonitrile 25%4-(trans-4-pentylcyclohexyl)-4′-cyanobiphenyl 15%

has the following values of physical properties.

NI:71.7, Δ∈:11.0, Δn:0.137, η:26.7, Vth:1.78.

The values of physical properties of liquid crystal composition (B)comprising of this composition (A) 85% and4″-propyl-2′,6′,3-trifluoro-4-trifluoromethoxyterphenyl (compound No.1)obtained at Example 1 15% are shown as follows.

Δ∈: 12.9, Δn: 0.144, η: 31.3, Vth: 1.51.

Although this liquid crystal composition (B) was left in a freezer at20° C., the appearance of a smectic phase and the deposition of crystalswere not found after 60 days.

EXAMPLE 3

(Using example 2)

Using the same method as described in Example 1, the following compoundcan be synthesized. Moreover, the values of physical properties weremeasured by using the same method as in Example 2.

Compound No.2: 5-B(F,F)BB(F,F)—F

Compound No.3: 2-B(F,F)BB(F,F)—OCF₃

Compound No.4: 4-B(F,F)BB(F)—OCF₃

Compound No.5: 1-B(F,F)BB—OCF₃

Compound No.6: 10-B(F,F)BB(F,F)—OCF₂H

Compound No.7: 3-B(F,F)BB(F)—OCF₂H

Compound No.8: 6-B(F,F)BB—OCF₂H

Compound No.9: 5-B(F,F)BB(F,F)—CF₃

Compound No.10: 4O—B(F,F)BB—CF₃

Compound No.11: 7-B(F,F)BB(F,F)—CF₂H

Compound No.12: 3O1-B(F,F)BB—CF₂H

Compound No.13:20-B(F,F)BB(F)—CFH₂

Compound No.14: 3-B(F)B(F)B(F,F)—F

Δ∈:11.9, Δn:0.140, η:27.1

Compound No.15: 4-B(F)B(F)B(F)—F

Compound No.16: 5-B(F)B(F)B(F,F)—OCF₃

Compound No.17: 6-B(F)B(F)B(F)—OCF₃

Compound No.18: 3-B(F)B(F)B(F,F)—OCF₂H

Δ∈:13.3, Δn:0.140, η:30.1

Compound No.19: 1-B(F)B(F)B(F)—OCF₂H

Compound No.20: 2-B(F)B(F)B—OCF₂H

Compound No.21: 5-B(F)B(F)B(F,F)—CF₃

Compound No.22: 3-B(F)B(F)B(F,F)—CF₂H

Compound No.23: 7-B(F)B(F)B(F)—CF₂H

Compound No.24: 12-B(F)B(F)B—CF₂H

Compound No.25: 1O₃O—B(F)B(F)B(F,F)—CFH₂

Compound No.26: 3-BB(F,F)B(F,F)—F

Δ∈:13.4, Δn:0.141, η:34.3

Compound No.27: 3-BB(F,F)B(F,F)—OCF₃

Δ∈:13.5, Δn:0.141, η:34.0

Compound No.28: 3-BB(F,F)B(F)—OCF₃

∈:13.5, Δn:0.142, η:34.0

Compound No.29: 3-BB(F,F)B(F,F)—OCF₂H

Compound No.30: 5-BB(F,F)B(F)—OCF₂H

Compound No.31: 7-BB(F,F)B—OCF₂H

Compound No.32: 9-BB(F,F)B(F,F)—CF₃

Compound No.33: 3-BB(F,F)B(F)—CF₃

Δ∈:13.5, Δn:0.142, η:34.0

Compound No.34: 2-BB(F,F)B(F,F)—CFH₂

Compound No.35: 4-BB(F,F)B(F)—CF₂H

Compound No.36: 6-BB(F,F)B—CF₂H

Compound No.37: 1O5-BB(F,F)B(F)—CFH₂

Compound No.38: 3-B(F,F)B(F)B(F,F)—F

Compound No.39: 5-B(F,F)B(F)B(F)—F

Compound No.41: 3-B(F,F)B(F)B(F,F)—CL

Compound No.42: 5-B(F,F)Be:B,F)—OCF₃

Compound No.43: 4-B(F,F)B(F)B(F)—OCF₃

Compound No.44: 12O1-B(F,F)B(F)B—OCF₃

Compound No.45: 2-B(F,F)B(F)B(F,F)—OCF₂H

Compound No.46: 3-B(F,F)B(F)B(F)—OCF₃H

Compound No.47: 6-B(F,F)B(F)B—OCF₂H

Compound No.48: 10-B(F,F)B(F)B(F,F)—CF₃

Compound No.49: 3-B(F,F)B(F)B(F)—CF₃

Δ∈:14.1, Δn:.0.137, η:30.9

Compound No.50: 5O1O—B(F,F)B(F)B(F,F)—CF₂H

Compound No.51: 7O—B(F,F)B(F)B(F)—CF₂H

Compound No.52: 4-B(F,F)B(F)B(F,F)—CFH₂

Compound No.53: 5-B(F)B(,F)B(F,F)—F

Compound No.54: 3-B(F)B(F,F)B(F)—F

Δ∈:12.8, Δn:0.141, η:29.3

Compound No.55: 4-B(F)B(F,F)B—F

Compound No.56: 6-B(F)B(F,F)B(F,F)—CL

Compound No.57: 3-B(F)B(F,F)B(F)—CL

Δ∈:13.3, Δn:0.148, η:33.4

Compound No.58: 14-B(F)B(F,F)B—CL

Compound No.59: 2-B(F)B(F,F)B(F,F)—OCF₃

Compound No.60: 6-B(F)B(F,F)B(F)—OCF₃

Compound No.61: 1O—B(F)B(F,F)B—OCF₃

Compound No.62: 7-B(F)B(F,F)B(F,F)—OCF₂H

Compound No.63: 3-B(F)B(F,F)B(F)—OCF₂H

Compound No.64: 3-B(F)B(F,F)B—OCF₂H

Compound No.65: 5-B(F)B(F,F)B(F,F)—CF₃

Compound No.66: 9-B(F)B(F,F)B(F)—CF₃

Compound No.67: 2O2-B(F)B(F,F)B—CF₃

Compound No.68: 4-B(F)B(F,F)B(F,F)—CF₂H

Compound No.69: 5-B(F)B(F,F)B(F)—CF₂H

Compound No.70: 5-B(F)B(F,F)B—CF₂H

Compound No.71: 3-B(F)B(F,F)B(F)—CFH₂

Compound No.72: 4-B(F,F)B(F,F)B(F,F)—F

Compound No.73: 5-B(F,F)B(F,F)B(F)—F

Compound No.74: 50-B(F,F)B(F,F)B—F

Compound No.75: 3-B(F,F)B(F,F)B(F,F)—CL

Compound No.76: 5-B(F,F)B(F,F)B(F)—CL

Compound No.77: 3-B(F,F)B(F,F)B(F,F)—OCF₃

Δ∈:15.3, Δn:0. 140, η:31.8

Compound No.78: 5-B(F,F)B(F,F)B(F)—OCF₃

Compound No.79: 2-B(F,F)B(F,F)B(F,F)—OCF₂H

Compound No.80: 3-B(F,F)B(F,F)B(F)—OCF₂H

Compound No.81: 4-B(F,F)B(F,F)B—OCF₂H

Compound No.82: 5-B(F,F)B(F,F)B(F,F)—CF₃

Compound No.83: 6-B(F,F)B(F,F)B(F)—CF₃

Compound No.84: 7B(F,F)B(F,F)B—CF₃

Compound No.85: 2-B(F,F)B(F,F)B(F,F)—CF₂H

Compound No.86: 3-B(F,F)B(F,F)B(F)—CF₂H

Compound No.87: 5-B(F,F)B(F,F)B—CF₂H

Compound No.88: 1O3-B(F,F)B(F,F)B(F,F)—CF₂H

EXAMPLE 4

(Using example 3)

The values of physical properties of liquid crystal compositions of theabove composition example 1 were as follows:

NI:83.8, Δ∈:10.5, Δn:0.159, η:23.9, Vth:1.48

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 5

(Using example 4)

The values of physical properties of liquid crystal compositions of theabove composition example 2 were as follows:

NI:86.3, Δ∈:9.7, Δn:0.163, η:23.1, Vth:1.85

Although the liquid crystal composition was left in a freezer at −20°C., the appearance of a smectic phase and the deposition of crystalswere not found after 60 days.

EXAMPLE 6

(Using example 5)

The values of physical properties of liquid crystal compositions of theabove composition example 3 were as follows:

NI:93.3, Δ∈:30.3, Δn:0.152, η:87.2, Vth:0.95

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 7

(Using example 6)

The values of physical properties of liquid crystal compositions of theabove composition example 4 were as follows:

NI:83.6, Δ∈:7.1, Δn:0.199, η:37.4, Vth:2.12

Although the liquid crystal composition was left in a freezer at −20°C., the appearance of a smectic phase and the deposition of crystalswere not found after 60 days.

EXAMPLE 8

(Using example 7)

The values of physical properties of liquid crystal compositions of theabove composition example 5 were as follows: NI:66.6, Δ∈:11.5, Δn:0.132,η:40.3, Vth:1.30

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 9

(Using example 8)

The values of physical properties of liquid crystal compositions of theabove composition example 6 were as follows:

NI:74.3, Δ∈:10.3, Δn:0.144, η:24.4, Vth:1.23

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 10

(Using example 9)

The values of physical properties of liquid crystal compositions of theabove composition example 7 were as follows:

NI:77.5, Δ∈:22.5, Δn:0.118, η:22.5, Vth:1.17

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 11

(Using example 10)

The values of physical properties of liquid crystal compositions of theabove composition example 8 were as follows:

NI:93.5, Δ∈:6.2, Δn:0.121, η:18.1, Vth:1.74

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 12

(Using example 11)

The values of physical properties of liquid crystal compositions of theabove composition example 9 were as follows:

NI:83.8, Δ∈:29.2, Δn:0.140, η:42.7, Vth:0.76

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 13

(Using example 12)

The values of physical properties of liquid crystal compositions of theabove composition example 10 were as follows:

NI:59.4, Δ∈:10.9, Δn:0.118, η:28.7, Vth:1.18

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 14

(Using example 13)

The values of physical properties of liquid crystal compositions of theabove composition example 11 were as follows:

NI:67.3, Δ∈:7.5, Δn:0.160, η:24.1, Vth:1.52

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 15

(Using example 14)

The values of physical properties of liquid crystal compositions of theabove composition example 12 were as follows:

NI:98.5, Δ∈:6.2, Δn:0.097, η:26.6, Vth:2.01

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 16

(Using example 15)

The values of physical properties of liquid crystal compositions of theabove composition example 13 were as follows:

NI:87.1, Δ∈:4.3, Δn:0.097, η:19.7, Vth:2.44

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 17

(Using example 16)

The values of physical properties of liquid crystal compositions of theabove composition example 14 were as follows:

NI:75.2, Δ∈:10.5, Δn:0.128, η:28.7, Vth:1.29

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 18

(Using example 17)

The values of physical properties of liquid crystal compositions of theabove composition example 15 were as follows:

NI:67.6, Δ∈:10.9, Δn:0.092, η:30.2, Vth:1.22

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 19

(Using example 18)

The values of physical properties of liquid crystal compositions of theabove composition example 16 were as follows:

NI:67.4, Δ∈:15.7, Δn:0.105, η:37.8, Vth:1.05

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 20

(Using example 19)

The values of physical properties of liquid crystal compositions of theabove composition example 17 were as follows:

NI:86.3, Δ∈:7.4, Δn:0.138, η:22.1, Vth:1.92

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 21

(Using example 20)

The values of physical properties of liquid crystal compositions of theabove composition example 18 were as follows:

NI:90.5, Δ∈:12.0, Δn:0.134, η:37.7, Vth:1.14

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 22

(Using example 21)

The values of physical properties of liquid crystal compositions of theabove composition example 19 were as follows:

NI:81.4, Δ∈:6.3, Δn:0.098, η:16.9, Vth:1.98

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 23

(Using example 22)

The values of physical properties of liquid crystal compositions of theabove composition example 20 were as follows:

NI:63.1, Δ∈:9.9, Δn:0.096, η:27.5, Vth:1.34

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

EXAMPLE 24

(Using example 23)

The values of physical properties of liquid crystal compositions of theabove composition example 21 were as follows:

NI:92.4, Δ∈:8.8, Δn:0.142, η:37.4, Vth:1.64

Although the liquid crystal composition was left in a freezer at 20° C.,the appearance of a smectic phase and the deposition of crystals werenot found after 60 days.

Industrial Applicability

The liquid crystalline compounds of the present invention have a veryhigh voltage holding ratio, a low threshold voltage, very littlevariation of these properties depending on temperature, and high Δn, andthe compatibility of these compounds with the other liquid crystalmaterials is improved. Further, new liquid crystalline compounds havingnecessary physical properties can be provided from the crystallinecompounds of the present invention by optional selection of substitutedgroups.

Accordingly, new liquid crystal compositions having a very high voltageholding ratio, very little variation of this property depending ontemperature, a low threshold voltage, appropriate Δn and Δ∈, stability,and excellent compatibility with other liquid crystal materials can beprovided by using the liquid crystalline compounds of the presentinvention as components of liquid crystal compositions. Moreover, liquidcrystal display devices constituted by using these can be provided.

What is claimed is:
 1. The terphenyl derivative represented by formula(1):

wherein R represents a straight or branched alkyl group of 1-10 carbonatoms, and any methylene groups (—CH₂—) not adjacent each other in eachalkyl group may be replaced by oxygen atoms; X represents a halogenatom, —OCF₃, —OCF₂H, —CF₃, —CF₂H or CFH₂; Y₁, Y₂, Y₃, Y₄, Y₅, and Y₆independently represents H or F, but at least two of Y₁, Y₂, Y₃ and Y₄represent F and one of Y₅ and Y₆ represents F and the other representsH; provided that a) when Y₁═Y₂═F and Y₃═Y₄═H, then X is not F, —CF₃ orCF₂H, b) when Y₁═Y₃═F and Y₂═Y₄═H, then X is not —CF₃, c) when Y₃═Y₄═Fand Y₁═Y₂═H, then X is not F, d) when Y₁═Y₂═Y₃═F and Y₄═H, then X is notCl, however, when Y₁═Y₂═F and Y₃═Y₄═H, when Y₁═Y₃═F and Y₂═Y₄═H, or whenY₃═Y₄═F and Y₁═Y₂═H, then X is not Cl.
 2. The terphenyl derivativeaccording to claim 1, wherein Y₁═Y₂═F, Y₃═Y₄═H and X═—OCF₃ or —OCF₂H. 3.The terphenyl derivative according to claim 1, wherein Y₁═Y₃═F, Y₂═Y₄═Hand X═—OCF₂H or —CF₂H.
 4. The terphenyl derivative according to claim 1,wherein Y₁═Y₃═Y₅═F, Y₂═Y₄═H and X═F or —OCF₃.
 5. The terphenylderivative according to claim 1, wherein Y₃═Y₄═F, Y₁═Y₂═H, and X═—OCF₂Hor —CF₂H.
 6. The terphenyl derivative according to claim 1, whereinY₃═Y₄═Y₅═F and Y₁═Y₂═H, and X═—OCF₃ or —CF₃.
 7. The terphenyl derivativeaccording to claim 1, wherein Y₁═Y₂═Y₃═F, Y₄═H, and X═—OCF₃ or —OCF₂H.8. The terphenyl derivative according to claim 1, whereinY₁═Y₂═Y₃═Y₅═Y₆═F, Y₄═H, and X═Cl.
 9. The terphenyl derivative accordingto claim 1, wherein Y₁═Y₂═Y₃═Y₅═F, Y₄═H, and X═F, —CF₃ or —CF₂H.
 10. Theterphenyl derivative according to claim 1, wherein Y₁═Y₃═Y₄═F, and Y₂═H.11. The terphenyl derivative according to claim 1, whereinY₁═Y₂═Y₃═Y₄═F, and X═F, —OCF₂H, —CF₃ or —CF₂H.
 12. The terphenylderivative according to claim 1, wherein Y₁═Y₂═Y₃═Y₄═Y₅═F, and X═Cl or—OCF₃.
 13. A liquid crystal composition, comprising at least one of theterphenyl derivatives described in claim
 1. 14. A liquid crystalcomposition, comprising as a first component thereof at least onederivative selected from the terphenyl derivatives described in claim 1,and as a second component thereof at least one compound selected fromthe group consisting of the compounds represented by formula (2), (3) or(4):

wherein R₁ represents an alkyl group of 1-10 carbon atoms, anyonadjacent methylene groups in the said alkyl group may be substitutedby oxygen atoms or —CH═CH—, and any hydrogen atoms in the alkyl groupmay be substituted by fluorine atoms; X₁ represents a fluorine atom, achlorine atom, —OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂, —OCF₂CF₂H or—OCF₂CFHCF₃; L₁ and L₂ independently represent a hydrogen atom or afluorine atom; Z₄ and Z₅ independently represent a 1,2-ethylene group,1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, —CH═CH—or a covalent bond,ring B represents trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or1,4-phenylene whose hydrogen atoms may be substituted by fluorine atoms;ring C represents trans-1,4-cyclohexylene, or 1,4-phenylene whosehydrogen atoms may be substituted by fluorine atoms.
 15. A liquidcrystal composition, comprising as a first component thereof at leastone compound selected from the compounds described in claim 1, and as asecond component thereof at least one compound selected from the groupconsisting of the compounds represented by formula (5) or (6):

wherein R₂ and R₃ independently represent an alkyl group of 1-10 carbonatoms, any nonadjacent methylene groups in the said alkyl group may besubstituted by oxygen atoms or —CH═CH—, and any hydrogen atoms in thealkyl group may be substituted by fluorine atoms; X₂ represents —CNgroup or —C≡C—CN; ring D represents trans-1,4-cyclohexylene,1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; ring Erepresents trans-1,4-cyclohexylene, 1,4-phenylene whose hydrogen atomsmay be substituted by fluorine atoms, or pyrimidine-2,5-diyl; ring Frepresents trans-1,4-cyclohexylene or 1,4-phenylene; Z₆ represents a1,2-ethylene group, —COO— or a covalent bond; L₃, L₄ and L₅independently represent a hydrogen atom or a fluorine atom; b, c and dindependently represent 0 or
 1. 16. A liquid crystal composition,comprising as a first component thereof at least one compound selectedfrom the compounds described in claim 1, as a second component thereofat least one compound selected from the group consisting of thecompounds represented by formula (2), (3) or (4),

wherein R₁ represents an alkyl group of 1-10 carbon atoms, anynonadjacent methylene groups in the said alkyl group may be substitutedby oxygen atoms or —CH═CH—, and any hydrogen atoms in the alkyl groupmay be substituted by fluorine atoms; X₁ represents a fluorine atom, achlorine atom, —OCF₃, —OCF₂H, —CF₃, CF₂H, —CFH₂, —OCF₂CF₂H or—OCF₂CFHCF₃; L₁ and L₂ independently represent a 1,2-ethylene group,1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, —CH═CH— or a covalent bond,ring B represents trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or1,4-phenylene whose hydrogen atoms may be substituted by fluorine atoms;ring C represents trans-1,4-cyclohexylene, or 1,4-phenylene whosehydrogen atoms may be substituted by fluorine atoms and as a thirdcomponent thereof at least one compound selected from the groupconsisting of the compounds represented by [general] formula (7), (8) or(9):

wherein R₄ and R₅ independently represent an alkyl group of carbon atomsof 1-10, any nonadjacent methylene groups in the said alkyl group may besubstituted by oxygen atoms or —CH═CH—, and any hydrogen atoms in thealkyl group may be substituted by fluorine atoms; ring G, ring I andring J independently represent trans-1,4-cyclohexylene,pyrimidine-2,5-diyl, or 1,4-phenylene whose hydrogen atoms may besubstituted by fluorine atoms; Z₇ and Z₈ independently represent —C≡C—,—COO—, —CH₂CH₂—, —CH═CH— or a covalent bond.
 17. A liquid crystalcomposition, comprising as a first component thereof at least onecompound selected from the compounds described in claim 1, as a secondcomponent thereof at least one compound selected from the groupconsisting of the compounds represented by the formula (5) or (6),

wherein R₂ and R₃ independently represent an alkyl group of 1-10 carbonatoms, any nonadjacent methylene groups in the said alkyl group may besubstituted by oxygen atoms or —CH═CH—, and any hydrogen atoms in thealkyl group may be substituted by fluorine atoms; X₂ represents —CNgroup or —C≡C—CN; ring D represents trans-1,4-cyclohexylene,1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; ring Erepresents trans-1,4-cyclohexylene, 1,4-phenylene whose hydrogen atomsmay be substituted by fluorine atoms, or pyrimidine-2,5-diyl; ring Frepresents trans-1,4-cyclohexylene or 1,4-phenylene; Z₆ represents a1,2-ethylene group, —COO— or a covalent bond; L₃, L₄ and L₅independently represent a hydrogen atom or a fluorine atom; b, c and dindependently represent 0 or 1, as a third component thereof at leastone compound selected from the group consisting of the compoundsrepresented by the formula (7), (8) or (9)

wherein R₄ and R₅ independently represent an alkyl group of carbon atomsof 1-10, any nonadjacent methylene groups in the said alkyl group may besubstituted by oxygen atoms or —CH═CH—, and any hydrogen atoms in thealkyl group may be substituted by fluorine atoms; ring G, ring I andring J independently represent trans-1,4-cyclohexylene,pyrimidine-2,5-diyl, or 1,4-phenylene whose hydrogen atoms may besubstituted by fluorine atoms; Z₇ and Z₈ independently represent —C≡C—,—COO—, —CH₂CH₂—, —CH═CH— or a covalent bond.
 18. A liquid crystalcomposition, comprising as a first component thereof at least onecompound selected from the compounds described in any claim 1, as asecond component thereof at least one compound selected from the groupconsisting of the compounds represented by the formula (2), (3) or (4),

wherein R₁ represents an alkyl group of 1-10 carbon atoms, anynonadjacent methylene groups in the said alkyl group may be substitutedby oxygen atoms or —CH═CH—, and any hydrogen atoms in the alkyl groupmay be substituted by fluorine atoms; X₁ represents a fluorine atom, achlorine atom, —OCF₃, —OCF₂H, —CF₃, CF₂H, —CFH₂, —OCF₂CF₂H or—OCF₂CFHCF₃; L₁ and L₂ independently represent a 1,2-ethylene group,1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, —CH═CH— or a covalent bond,ring B represents trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or1,4-phenylene whose hydrogen atoms may be substituted by fluorine atoms;ring C represents trans-1,4-cyclohexylene, or 1,4-phenylene whosehydrogen atoms may be substituted by fluorine atoms, as a thirdcomponent thereof of at least one compound selected from the groupconsisting of the compounds represented by the formula (5) or (6),

wherein R₂ and R₃ independently represent an alkyl group of 1-10 carbonatoms, any nonadjacent methylene groups in the said alkyl group may besubstituted by oxygen atoms or —CH═CH—, and any hydrogen atoms in thealkyl group may be substituted by fluorine atoms; X₂ represents —CNgroup or —C≡C—CN; ring D represents trans-1,4-cyclohexylene,1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; ring Erepresents trans-1,4-cyclohexylene, 1,4-phenylene whose hydrogen atomsmay be substituted by fluorine atoms, or pyrimidine-2,5-diyl; ring Frepresents trans-1,4-cyclohexylene or 1,4-phenylene; Z₆ represents a1,2-ethylene group, —COO— or a covalent bond; L₃, L₄ and L₅independently represent a hydrogen atom or a fluorine atom; b, c and dindependently represent 0 or 1, as a fourth component thereof at leastone compound selected from the group consisting of the compoundsrepresented by the formula (7), (8) or (9)

wherein R₄ and R₅ independently represent an alkyl group of carbon atomsof 1-10, any nonadjacent methylene groups in the said alkyl croup may besubstituted by oxygen atoms or —CH═CH—, and any hydrogen atoms in thealkyl group may be substituted by fluorine atoms; ring G, ring I andring J independently represent trans-1,4-cyclohexylene,pyrimidine-2,5-diyl, or 1,4-phenylene whose hydrogen atoms may besubstituted by fluorine atoms; Z₇ and Z₈ independently represent —C≡C—,—COO—, —CH₂CH₂—, —CH═CH— or a covalent bond.
 19. A liquid crystalcomposition, comprising the liquid crystal composition described inclaim 13 and at least one optically active compound.
 20. A liquidcrystal comprising using the liquid crystal composition described inclaim 13.